Copolymers of unsaturated ethers and halogenated unsaturated ethers and method of preparing same



3,251,813 COPOLYMERS F UNSATURATED ETHERS AND HALOGENATED UNSATURATED ETI-IERS AND METHOD OF PREPARING SAME Giulio Natta, Mario Farina, and ,Giancarlo Bressan, Milan, Italy, assignors to Montecatini Societal Geuerale per; llndustria Mineraria e Chimica, a corporation of ta y No Drawing. Filed July 25, 1961, Ser- No. 128,302 Claims priority, application Italy, July 26, 1960,

13,317/ 60 27 Claims. '(Cl. 260-803) The present invention relates to copolymers of unsaturated ethers of the general formula wherein R is either hydrogen or an organic radical having from 1 to 16 carbon atoms and is selected from the group consisting of alkyl, alicyclic, aryl, and aralkyl and R is a radical having from 1 to 16 carbon atoms and is selected from the group consisting of alkyl, alicyclic, aryl, and aralkyl, with halogenated unsaturated ethers of the general formula wherein X is a halogen atom and R" is a radical having from '1 to 16 carbon atoms and is selected from the group consisting of alkyl, alicyclic, aryl, and aralkyl. The present invention also relates to a method for preparing the above mentioned copolymers' It is knownthat unsaturated ethers belonging to the class of vinyl and alkenyl ethers of the Formula 1 and to the class of the fi-halo-vinyl-ethers of Formula 2 are homopolymerizable in the presence of suitable ionic catalysts in a stereospecific manner.

Surprisingly it has now been found that in the presence of suitable catalysts it is possible to copolymerize monomers defined by Formula 1 with monomers defined by Formula 2 and that high molecular weight copolymers may be obtained, which copolymers exhibit interesting chemical and physical properties, e.g., the capacity to undergo vulcanization.

The fact that the products of the instant invention are in fact genuine copolymers and not a mechanical mixture of homopolymers is clearly demonstrated by X-ray examination. In fact, if a pure monomer of either Formula 1 or 2 herein is homopolymerized under the same conditions herein specified for copolymerization, crystalline polymers are generally obtained. If the monomer is a vinyl ether, the homopolymer will have an isotactic structure; if it is an alkenyl trans ether or a B-chloro-trans, vinyl ether, then a threodiisotactic structure; if a fi-chloro cis vinyl ether, an erythro-di-isotactic structure. Each such homopolymer has a characteristic X-ray dilfraction pattern and is powder or fiber like.

On the contrary, X-ray analysis of the copolymer products obtained by copolymerization according to the present invention, shows such copolymers to be either only partially crystalline, i.e., when one of the monomers (able to produce a crystalline homopolymer) is copolymerized with a small percentage (for instance, less than 10 mole percent) of the other monomer; or else rubber like or oil like and amorphous (when the monomer capable of producing a crystalling homopolymer is used in an amount less than 90 mole percent). The copolymerization may be carried out within a very wide Patented May 17, 1966 temperature range, generally from 120 to about +100 0., and preferably from about 100 to ;+20 C.

Among the catalysts which may be used according to the process of the present invention are compounds or mixtures of compounds having an attenuate cationic catalytic activity and selected from the group consisting of boron halides, complexed boron halides, e.g.

halides of metal organic compounds of metals from Groups II and III of the Periodic Table, halo-alcoholates and other mixed salts of transition metals of Group IV of the Periodic Table.

Among the compounds which have shown a high catalytic activity are included boron fluoride etherate, monoethylaluminum dichloride, diethylaluminium monochloride, dichlorotitanium dibutylate, and dichloro titanium diacetate.

According to the present invention the polymerization preferably is carried out in a solvent that is inert with respect to the catalyst system, for instance, toluene, heptane, or other low-boiling hydrocarbons. When boron fluoride etherate is employed as the catalyst, other organic compounds also may be used as solvents, for instance, ethers and esters.

The catalysts is generally added to a solution in an inert solvent of the two monomers, which are previously prepared and maintained at the desired temperature. Of course, the order of addition may be varied by introducing the monomers into a solution of the catalyst.

It is known that a copolymer composition, because of dilferent relative reactivities of its two starting monomers, is generally different from that of the mixture of the starting monomers, and that said composition generally varies as the conversion proceeds.

The subsequent examples show that the non-halogenated monomer is remarkably more reactive than the halogenated monomer. Therefore, when a copolymer having a specified composition is desired, it is necessary to employ a mixture having a halogenated monomer content higher than that which corresponds to the desired content of said monomer in the copolymer.

The composition of the monomer mixture which under stationary conditions gives a copolymer of the desired composition may be easily calculated when the relative reactivities r and r of the single monomers are experimentally determined.

When operating according to a batch-process it is advisable, in order to obtain a copolymer having a homogeneous composition, to start the reaction with a solution very rich in the halogenated monomer and then to add progressively a mixture of the monomers in amounts corresponding to the amount which has been polymerized for each monomer during the same period of time; this is equivalent to the addition of a mixture of the two monomers having composition and the weight equal to the weight of the copolymer thus formed. This procedure can be effected when the kinetic parameters of the reaction are known.

With a continuous process it is easier to obtain the desired stationary conditions and to obtain a homogeneous copolymer.

Due to the geometrical stereo-isomerism of some monomers to which the present invention relates, several types of copolymer are possible, according to particular com-. bination employed. In fact, the alkenyl ethers and the fl-halo-vinyl ethers exist in the cis and trans forms which can be distinctly separated and characterized.

Therefore, it is necessary to consider all the possible combinations of copolymers of vinyl ethers and of alkenyl 1y amorphous, still have a regular structure with respect to the alkoxy groups.

In particular, a copolymer of a vinyl. ether with a B- chloro vinyl ether, this copolymer having the same alkoxy ethers (in the two cis and trans series) both with the 5 substituents (and which may be considered as derived fl-halo vinyl ethers cis and with the trans isomers, and from the vinyl ether homopolymer by substitution of also with the raw cis-trans mixture obtained directly chlorine atoms for hydrogen atoms in CH groups from the synthesis. in the chain) exhibits, as compared with similar com-. The following monomers are illustrative of those which P h obtalhed by chlonhahoh soluhoh m the are included in Formulas l and 2. Monomers comprised absence of solvent) of the correpohdlhg Ph ether, in Formula 1 include; vinyl methyl ether vinyl ethyl remarkable dlfferences, as for instance, the presence of ether, vinyl propyl ether, vinyl isopropyl ether, vinyl chlorine atoms only m the main chain and, therefore, butyl ether, Vinyl isobutyl ether, vinyl cyclohexyl ether, :1 more regular distrrbutlon of the chlorine atoms in the vinyl phenyl ether, etc.; the two cis and trans series (or P mixtures thereof) of propenylmethyl ether, propenyl ethyl T lhtflhlsle vlseoslty therefore, the average fiber propenyl propyl ether, propenyl isopropyl ether, molecular welght) of the copolymers may be; remarkably propenyl butyl ether, propenyl isobutyl ether, propenyl increased by decreasing the rate of polymerization, e.g., phenyl ether, propenyl cyclohexyl ether, propenyl benby further l'owerlhg the p y e P zyl ether, butenyl methyl ether, butenyl ethyl ether, bute- The h 'f coholymers obthlhed accordlhg to the nyl isobutyl ether, cyclohexyl methoxy ethylene, phenyl present inventionrepresent a new class of products of methoxy ethylene, benzyl methoxy ethylene, remarkable technical interest. In fact, they are able to Monomfirs comprised in Formula 2 include; the two undergo vulcanization and may be converted into elastic cis and trans series (or mixtures thereof) of B-chloro P d ts having Very good mechanical ChZIaCtCI'lSUCS vinyl methyl ether, fi-chloro viny-l ethyl ether, 3-chl (e.g., high ultimate tensile stress and elastic elongation), vinyl propyl ether fichloro vinyl isopropyl ether, which products may be used in a wide variety of technical r0 vinyl butyl ether, ,B-chloro vinyl isobutyl ether, ,8- apphehhohe and Present, as cohfpared to dlolefih e chlom vinyl phmyl ether, #01110, vinyl cyclohexyl tomers, a higher stability and resistance to degradations, ether [Emblem vinyl benzyl ether vinyl methyl in particular, resistance to attack by the atmospheric ether, fl-bromo vinyl ethyl ether, fl-bromo vinyl butyl agentsether, p-brom'o vinyl isobutyl ether, fi-iodo vinyl methyl Examples ether vinyl butyl e vinyl isobutyl ether Solutions of the monomers are introduced into a dried The z f 3 hff ag g La copolymegs glass tube under nitrogen. After the desired tempera- 1??" no y y :g g: e f group t e ture is obtained, a solution or suspension of the catalyst a ogen e eon e Ion 0 e monomer? is added under nitrogen. A remarkable evolution of heat but also by varying the ratio between the monomeric is generally observed umts of the type (1) and those of the P (2) m the 9 After maintaining the mixture at constant temperature m In fact dependmg on the used e e for the required time, the contents of the glass tube are a gradual passage from products having characterlstics poured into methanol whichcause the copolymer to of h homopelyhner of one e to amorphous produets 40 agulate. The copolymer is dried for an extended period havmg Wholly ,dlfierent Propertles, Products havmg of time under vacuum at a moderate temperature and is the characteristics of the other homopolymer. Those finally weighed 32 33122 3 g g g g g g g l g jg g 2 5213 55%: The quantitative results are set forth in Table 1, wherein 10% by weight and f bl f o 1 to 5 which h and f are the molar fraction of the monomers A and corresponds to a fraction of monomeric units, derived the 1n1'11a1 f ia d from the monomers comprised in the general Formula 2, FB 15 the molar frachoh 9f monemelle llhlts B 111 the in the polymer less than 30% and preferably from about p y lto 1 0%. The intrinsic viscosity [1 is determined at 30 C. in

It is believed that such copolymers, even if occasionaltoluene; the values are expressed as X100 ml./ g.

TABLE I Monomers Polymerization conditions Example Monomer-A G. fA MonomerB G. In Solvent Cc.

percent percent Vinylisobutyletheni 1.0 28 fi-chlorovinylisobutylether 3.4 72 Toluene -----2:

a d r I do 4.0 86 0.85 55 Vinylbutylether 2.0 89 0.35 30 do 2.0 80 0. 0 7 do 2.0 66 1.40 30 8.... .....d 0.5 20 2.75 30 36 viny lisobutylether gilt fl-cgloro ygsolgufiyletgehtransmn 45 n -0 l'OVln G eI-CS 11 Methylisobutoxyethylenecis 3.0 88, g-clil rov'ing'liz biitg lether-ti-ans.. 0.5 12 Methylisobutoxyethylenetrans 0.85 87 '..d0 0.15 25 13-- .do 1.20 78 fl-ehlorovinylisobutylether-cis 0.4 25 14-- Methylisobutoxyethylene cis 3.05 79 do 0.95 45 15-- Viny1butylether 2.0 80 B-chIorovinylbutylether-eis 0.70 40 it?" vinyllisobutylether fl-chgrovinylisobutylether- 20 o. 0 30 1s (in 4.0 84 do 1.0 16 Diethylether 30 5g -.gg 2.8 31 gg... H; 16 Ethylacetate 2(5) 21I IIIIdo 5:6 84 IIIIIdoII 114 25 22 do 34.4 84 d0 8.6 25

TABLE IContinued Polymerization conditions Copolymer Example 7 Duration, h. Conversion, C1 in the polyfa Catalyst Cc. T., O. minutes Polymer, g. percent by mer, percent percent (1;)

- weight by weight AlClnCzHs 0. 1 75 45 0.29 6. 10. 4 32 N.D. A1C12C2H5- 0. 1 75 0 45 0. 50 11 5. 9 l7 N.D A1C12C2 5 0.1 75 0 45 1. 27 27 2.1 6 0.27 AlC12CzH 0.1 75 0 45 1.86 38. 5 1. 1 3 O. 3 AlClgCaH: 0. 05 75 0 1.11 47 0.7 2 N.D. A1CI2C2H5 0.05 75 0 30 0. 91 34 1.0 3 N.D. AlClzCzH: 0. 05 75 1 15 0. 83 2. 0 6 N.D. AICIZC'JHK 0. 05 75 2 0. 06 2 11.0 85 N.D. 0. 05 75 0 20 2. 38 62 0.15 0.5 N.D. 0. 05 75 0 30 3. 65 46 2.5 7 N.D. 0. O5 75 2 20 2.8 80 0.2 0.6 N.D. 0. 05 75 2 30 0.72 72 0. 3 1.0 0.23 0. 05 75 2 30 1. 84 4. 25 14 0. 28 0- 05 75 2 2. 88 72 0. 4 1. 3 N.D. 0. 2 75 1 15 2.13 79 3. 6 10 O. 29 0.5 +20 15 0. 48 12 3.0 9 N.D. 0. 1 20 1. 55 39 2. 4 '6. 5 0.21 0. 1 +20 80 3. 1 62 3. 3 9. 3 N.D. 0. 1 +20 80 0. 6 12 3. 7 10.7 N.D. 0. 1 75 0 50 1. 75 35 2. 3 6. 3 N.D. 0. 1 90 0 30 3.1 44 2. 2 6 0. 36 AlClzCzHs 0. 8 75 19 30. 6 72 2. 4 6. 7 0. 27

Variations can, of course, be made without departing from the spirit of this invention.

Having thus described this invention, what is desired to be secured and is hereby claimed is:

1. Linear amorphous copolymers of two unsaturated ether monomers having chlorine directly attached to the main chain, one of these monomers defined by the formula RCH=CH-OR wherein R is a member selected from the group consisting of hydrogen, CH and C H and R is an alkyl group having from 1 to 4 carbon atoms; the second of these monomers being an unsaturated halogenated ether defined by the formula wherein X is chlorine and R" is an alkyl group having from 1 to 4 carbon atoms.

2. The copolymer of claim 1 wherein the monomeric units derived from the unsaturated halogenated ether are present in the copolymer in a molar fraction less than 30%.

3. The copolymer of claim 2 wherein the monomeric units derived from the unsaturated halogenated ether are present in the copolymer for a molar fraction between 1 and 10%.

4. The copolymer of claim 1 wherein R is methyl.

5. The copolymer of claim 1 wherein R is butyl.

6. The copolymer of claim 1 wherein R is isobutyl.

7. The copolymer of claim 1 wherein R" is butyl.

8. The copolymer of claim 1 wherein R" is isobutyl.

9. A copolymer according to claim 1 of vinyl-isobutyl ether and fl-chloro vinylisobutyl ether.

10. A copolymer according to claim 1 of vinyl isobutyl ether and fl-chloro vinyl isobutyl ether cis.

11. A copolymer according to claim 1 of vinyl isobutyl ether and ,S-chloro vinyl isobutyl ether trans.

12. A copolymer according to claim 1 of vinyl butyl ether and fl-chloro vinyl butyl ether cis.

13. A copolymer according to claim 1 of methyl isobutoxy ethylene cis and ,fZ-chloro vinyl isobutyl ether cis.

14. A copolymer according to claim 1 of methyl isobutoxy ethylene cis and fi-chloro vinyl isobutyl ether trans.

15. A copolymer according to claim 1 of methyl isobutoxy ethylene trans and fl-chloro vinyl isobutyl ether trans.

16. A copolymer according to claim 1 of methyl isobutoxy ethyl trans and fi-chloro vinyl isobutyl ether cis.

17.'A process for the preparation of copolymers of claim 1 comprising copolymerizing the two monomers at a temperature from about 120 to C. in the presence of an effective amount of a catalyst comprising a compound selected from the group consisting of boron halides and complexes thereof, halides of organometallic compounds of metals belonging to Groups II and III of the Periodic Table, and halogeno-alcoholates of transition metals belonging to Group IV of the Periodic Table.

18. The process of claim 17 wherein the copolymerization is carried out at a temperature of from about 100 to +20 C.

19. The process of claim 17 wherein the copolymerization is carried out in the presence of a solvent which is inert with respect to the catalytic system and is selected from the group consisting of aliphatic and aromatic hydrocarbons, ethers, and esters.

20. The process of claim 19 wherein the inert solvent .is toluene.

References Cited by the Examiner UNITED STATES PATENTS 3,025,275 3/ 1962 Heck 360-803 FOREIGN PATENTS 571,741 4/ 1958 Italy.

OTHER REFERENCES Schwan et al., J. Polymer Science 40, 457-468 (1959). Shostakovskii et 211., CA. 45,2851 i (1951).

JOSEPH L. SCHOFER, Primary Examiner.

JOSEPH R. LIBERMAN, JAMES A. SEIDLECK,

Examiners. 

1. LINEAR AMORPHOUS COPOLYMERS OF TWO UNSATURATED ETHER MONOMERS HAVING CHLORINE DIRECTLY ATTACHED TO THE MAIN CHAIN, ONE OF THESE MONOMERS DEFINED BY THE FORMULA R-CH=CH-OR'' WHEREIN R IS A MEMBER SELECTED FROM THE GROUP CONSISTING OF HYDROGEN, CH3 AND C2H5 AND R'' IS AN ALKYL GROUP HAVING FROM 1 TO 4 CARBON ATOMS; THE SECOND OF THESE MONOMRS BEING AN UNSATURATED HALOGENATED ETHER DEFINED BY FORMULA 